PL98703B1 - INSECTICIDAL, MUSHROOM AND MUSHROOM AGENT - Google Patents
INSECTICIDAL, MUSHROOM AND MUSHROOM AGENT Download PDFInfo
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- PL98703B1 PL98703B1 PL1976190711A PL19071176A PL98703B1 PL 98703 B1 PL98703 B1 PL 98703B1 PL 1976190711 A PL1976190711 A PL 1976190711A PL 19071176 A PL19071176 A PL 19071176A PL 98703 B1 PL98703 B1 PL 98703B1
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- FAFAJVGGXSJIQX-UHFFFAOYSA-N tricyclohexyl(1h-1,2,4-triazol-5-yl)stannane Chemical compound C1CCCCC1[Sn](C=1NN=CN=1)(C1CCCCC1)C1CCCCC1 FAFAJVGGXSJIQX-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2284—Compounds with one or more Sn-N linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
Przedmiotem wynalazku jest srodek owadobój¬ czy, roztoczobójczy i grzybobójczy zawierajacy no¬ we l^trójiorga«iostannylo-2,4-dwuketo-l,2,3,4-cztero- wodoroHsym-triazyno-H^-alHbenzimidazole podsta¬ wione w polozeniu 3, jako substancje czynna.The present invention relates to an insecticide whether, acaricide and fungicide containing nova in the first three-octane-2,4-biceto-1,2,3,4-four- HydroHsim-triazine-H4 -alH-benzimidazoles substituted by placed at position 3 as active ingredient.
Wiadomo, ze niektóre zwiazki trójorganocyny maja dzialanie pestycydowe, na przyklad trójcy- klohelsylostaninyloibenziotariazol (opis patentowy St.It is known to have some trigorocin compounds have a pesticidal effect, for example, clohelsylstaninylbenziotariazole (US Patent No.
Zjedn. Am. nr 3 546 240), trójcyikloheksylostannylo- -1,2,4-triazol (opis patentowy RFN DAS nr 2143 252) i trójfenylostainnyloimidazol (opis paten¬ towy RFN DOS nr 2 056 652). Zakres i intensyw¬ nosc dzialania owadobójczego i roztoczobójczego tych zwiazków, zwlaszcza w nizszych dawkach, nie zawsze jednak sa zadawalajace. Wiadomo tez, ze estry alkilowe kwasu N-benzimidazolilo-(2)-kar- baminowego oraz zwiazki, które po zastosowaniu przeksztalcaja sie w estry alkilowe kwasu N-ben- zimidazolilo-(2)-karbaimiiniowego, maja dzialanie grzybobójcze (opisy patentowe RFN DOS nr Ij6|28,ir754 1746 764 i 1806123). Zwiazki te nie dzia¬ laja jednak lub dzialaja tylko slabo na Phycomy- cetes. Ponadto w ostatnich latach wytworzyla sie odpornosc przeciwko zwiazkom tego typu, co ogra¬ nicza bardzo mozliwosci ich stosowania.US Am. No. 3 546 240), tricyclohexylstannyl- -1,2,4-triazole (Germany's DAS patent no 2143 252) and triphenylstaininylimidazole (US Pat German DOS No. 2 056 652). Scope and intensity Insecticidal and acaricidal activity these compounds, especially at lower doses, however, they are not always satisfactory. It is also known with N-benzimidazolyl- (2) -car- acid alkyl esters bamin and compounds that when applied they transform into alkyl esters of N-ben- Zimidazolyl- (2) -carbaimine, they have an effect fungicides (German patents DOS no Ij6 | 28, ir754 1746 764 and 1806123). These compounds are not working however, or act only weakly on Phycoma- cetes. In addition, it has developed in recent years resistance to compounds of this type that will limit them there is very little possibility of using them.
Stwierdzono, ze nowe podstawione w pozycji 3 lHtrójorgainoistannyilo^^^dwuketo-l^jS^^zterowo- doronsymHtriazynb [ili^^l-lbenziarniidazole o wzorze 1, w którym R1 oznacza prosty lub rozgaleziony rod¬ nik^ alkilowy, rodnik cyMoalkilowy o 4—8 ato^ mach wegla lub rodnik fenylowy, R2 oznacza rod¬ nik alkilowy o 1—18 atomach weigla, ewentualnie podstawiony atomem chloru, grupa CN, rodnikiem fenylowym, grupa alkokisykarbonylowa o 1—5 ato¬ mach wegla w czesci alkokisylowej, grupa alkeno- ksykarbonylowa zawierajaca do 5 atomów wegla w czesci alkenoksylowej, grupa alkiloaminokarbo- nyiow^ o 1—6 atomach wegla w czesci alkiloami- nojwej, grupa Nnmorfolinylowa lub nizsza grupa dwualkiloaminowa lub oznacza nizsza grupe dwu- alkiloamiaiowa albo rodinik cykloheksylowy lub fe¬ nylowy, maja silne dzialanie owadobójcze, rozto- czobójcze i grzybobójcze.It was found that the new substituted in position 3 lHtrorganeseistannyilo ^^^ two-eo-l ^ jS ^^ ztero- doronsymHtriazinib [ili ^^ l-lbenziarniidazoles of formula 1, wherein R1 is straight or branched rhodium alkyl group, 4-8% aminoalkyl radical carbon or phenyl radical, R2 is rhodium an alkyl group of 1-18 carbon atoms, optionally substituted with chlorine atom, CN group, radical phenyl, an alkoxysycarbonyl group of 1-5 atom carbon scuff in the alkoxysyl part, the alkene group xycarbonyl with up to 5 carbon atoms in the alkenoxy part, the alkylaminocarbo- low carbon with 1 to 6 carbon atoms in the alkylamino portion Nnmorpholinyl or a lower group dialkylamino or di-lower group alkylamino or cyclohexyl radical or phen nylon, have a strong insecticidal effect, melt suicidal and fungicidal.
Zwiazki o wzorze 1 otrzymuje sie przez reakcje ewentualnie zawierajacych rozpuszczalnik soli me¬ tali alkalicznych, metali ziem alkalicznych lub so¬ li amonowych podstawionego w polozeniu 3 2,4- -dwuketo-l^yS^-iczterowodoro-sym^triazyino-ri^- -a]-benzimddazolu o wzorze 2, w którym R2 ma, wyzej podane znaczenie, X oznacza równowaznik jonu metalu alkalicznego lub metalu ziem alka¬ licznych albo oznacza grupe [HNR33]+ lub [NR84]+, a R3 oznacza organiczne grupy silnie zasadowego jonu amoniowego, z halogenkami trójorganocyny o wzorze 3, w którym R1 ma wyzej podane zna¬ czenie, a Hal oznacza atom choru, bromu lub jo¬ du.The compounds of formula I are obtained by reactions optionally solvent-containing salts of metals of alkali, alkaline earth metals or sodium l and ammonium substituted in position 3 2,4- -Duketo-l ^ yS ^ -tetrahydro-sym ^ triazino-ri ^ - - a] -benzimddazole of formula 2, wherein R2 has, the meaning given above, X is equivalent to alkali metal or alkaline earth metal ion multiple or represents the group [HNR33] + or [NR84] +, and R3 represents strong basic organic groups ammonium ion, with triorganotin halides of Formula III in which R 1 has the above-mentioned names and Hal is chlorine, bromine or io du.
Nowe 1 -trój orgainostannylo-2,4-dwuketo-l,2,3,4- ^czterowiodoroHsyim-triazyino-[l,2-a]Hbenizimiidazotle podstawione w polozeniu 3 maja znacznie lepsze 987033 98703 4 dzialanie owadobójcze, roztoczobójcze i grzybobój¬ cze, niz znane ze stanu techniki trójorganostanny- loazóle. Oprócz tego zwiazki te dzialaja bardzo skutecznie na owady i roztocza, które juz uodpor¬ nily sie. w' znacznym stopniu na estry kwasu fo¬ sforowego. Nowe zwiazki wychodza zatem naprze¬ ciw pilnemu zapotrzebowaniu na zwiazki • lepsze i o innym charakterze dzialania. Wzbogacaja one wiec stan techniki.Novel 1-three-orgainostannyl-2,4-biceto-1,2,3,4- ^ tetrahydroHsyim-triazino- [1,2-a] Hbenizimiid nitrogen placed on May 3, much better 987033 98703 4 insecticidal, acaricidal and fungicidal activity than the three organostans known from the state of the art loazole. Besides, these compounds work a lot effective against insects and mites that are already resistant nily. largely to the esters of the pho stuffy. The new relationships therefore come forward in urgent need for better relationships and of a different nature of action. They enrich so the state of the art.
Zwiazki triazynobenzimidazolocyny o wzorze 1 maja równiez- dobre dzialanie grzybobójcze. Dzia¬ laja one na szkodliwe grzyby podatne na dziala¬ nie estrów alkilowych kwasu N-benzimidazolilo- -(2)-karbaminowego i zwiazków pokrewnych oraz na szczepy odporne. Ponadto mozna je stosowac do zwalczania grzybów klasy Phycomycetes.The triazinobenzimidazolocin compounds of the formula I they also have a good fungicidal effect. Action they attack harmful fungi susceptible to the action non-alkyl esters of N-benzimidazolyl- - (2) -carbamic acid and related compounds and to resistant strains. Moreover, they can be used for the control of Phycomycetes class fungi.
Pod wzgledem sily dzialania grzybobójczego przewyzszaja one niespodziewanie znane trójor- ganylostannyloazole. Ze wzgledu na szczególnie szerokie spektrum dzialania biologicznego sa one cennym wzbogaceniem stanu techniki. Ponadto ze wzgledu na wysoki ciezar czasteczkowy skladnika triazynobenzimidazolowego zawartosc cyny w sub¬ stancjach czynnych jest stosunkowo nieznaczna, co stanowi ich zalete, poniewaz cyna nie nalezy do pierwiastków dostepnych w dowolnej ilosci i jej oszczedne uzycie jest wskazane.In terms of the strength of the fungicidal action they surpass the unexpectedly known three-way ganylostannyloazole. For the sake of especially a broad spectrum of biological activity they are valuable enrichment of the state of the art. Moreover, with due to the high molecular weight of the ingredient triazinobenzimidazole tin content in the sub active stations is relatively insignificant, co is their advantage because tin does not belong to elements available in any quantity and her economical use is advisable.
W przypadku stosowania soli sodowej 3-co-cyja- nopentylq-2,4^dwuketo-'l,2,3,4-czterowodoro-sym- -triazyno-[l,2^a]- benzimidazolu i chlorku trójbu- tylocyny jako substancji wyjsciowych, przebieg re¬ akcji przedstawia schemat 1.When using the sodium salt of 3-co-cyja- nopentylq-2,4- diceto--1,2,3,4-tetrahydro-sym- -triazino- [1,2 ^ a] - benzimidazole and tribium chloride tylocin as starting substances, the course of re¬ action is shown in the diagram 1.
Substancje wyjsciowe przedstawiaja ogólnie wzory 2 i 3, w których R1 oznacza korzystnie rod¬ nik butylowy, cykloheksylowy, n-oktylowy i feny- lowy, a R2 oznacza korzystnie rodnik alkilowy o \—5t io lub 11 atomach, wegla, ewentualnie pod¬ stawiony w polozeniu co grupa CN, alkoksykarbo- nylowa o 1—4 atomach wegla w czesci alkoksy- lowej, grupa alkenoksykarboinylowa o 2—4 ato¬ mach wegla w czesci alkenoksylowej, grupa N- -tmorfolinowa, dwualkiloaminowa o 2—4 atomach wegila w kazdym rodniku alkiowym lub oznacza grupe dwualkiloaminowa o 2—4 atomach wegla w kazdym rodniku alkilowym, X oznacza korzyst¬ nie jon metalu alkalicznego.The starting substances are presented overall formulas 2 and 3 in which R1 is preferably rhodium butyl, cyclohexyl, n-octyl nickel and phe- preferably, R2 is preferably an alkyl radical There are 5 to 5 carbon or 11 carbon atoms, optionally positioned as the CN group, alkoxycarbo- nylon with 1-4 carbon atoms in the alkoxy part a 2 to 4 atom alkenoxycarboinyl group carbon in the alkenoxy part, group N- -tmorpholino, dialkylamino of 2 to 4 atoms carbonated in each alkyl radical or means dialkylamino group with 2 to 4 carbon atoms in each alkyl radical, X is preferably not an alkali metal ion.
Szczególnie korzystne sa zwiazki, w których R1 oznacza rodnik butylowy lub cykloheksylowy, a R2 oznacza rodnik: butylowy, co-cyjanoalkilowy lub cy-alkoiksykarbonyloalkilowy o 1—11 atomach we¬ gla w lancuchu alkilenowym, rodnik propylowy podstawiony grupa N-morfóliiny oraz grupa dwu- metyloaminowa. 2,4-dwuketo-l,2,3,4-czterowodoro-sym-triazyno- -[l,2-a]-benzimidazole podstawione w polozeniu 3 sa czesciowo znane z opisu RFN DOS nr 2144 505.Compounds in which R1 is a butyl or cyclohexyl radical and R2 represents the radical: butyl, ω-cyanoalkyl or cy-alkoxycarbonylalkyl of 1-11 bn atoms carbon in the alkylene chain, propyl radical substituted N-morpholiin group and two- methylamine. 2,4-biceto-1,2,3,4-tetrahydro-sym-triazine- - [1,2-a] benzimidazoles substituted at the 3-position are partially known from the German description DOS No. 2144 505.
Nowe zwiazki o wzorze 1 mozna wytworzyc we¬ dlug sposobu podanego w wymienionym opisie.The new compounds of formula I can be prepared by the debt of the method described in the said description.
Mozna je równiez wytworzyc przez cyklizacje pod¬ stawionych w polozeniu 3 l-(benzimidazolilo-2)- --moczników droga dzialania weglanu dwufenylo- wego w temperaturze 140^220°C, korzystnie 160— 190°C wedlug schematu 2.They can also be produced by cyclization of the subs placed in position 3 l- (benzimidazolyl-2) - - ureas the route of action of diphenyl carbonate at a temperature of 140-220 ° C, preferably 160- 190 ° C according to diagram 2.
Podstawione w polozeniu 3 14benaimidazolilo-2)- -mocznifci sa po czesci znaine z opisu patentowego St. Zjedn. Am. nr 3 399 212 lub mozna je wytwo¬ rzyc wedlug sposobu podanego w tym opisie. ' Do reakcji wprowadza sie np. nizej podane zwiazki wyjsciowe o wzorach 2 i 3: sole sodowe, potasowe, litowe, wapniowe, magnezowe, stronto¬ we i barowe lub trójmetylo-, trójetylo-, benzylo- dwumetylo-, cykloheksylodwumetyilo-, lub dodecy- lotrójmetyloamoniowe, 3-co-cyjainoetylo-, 3-co-cyja- nopentylo-, 3-co-cyjanopentylo-5- lub -6-metylo-, 3-ctf-cyjariopentylo-5- lub -6-butylo-, 3-w-cyjano- pentylo-4- lub -7-metylo-, 3-w^cyjanoundecylo-, 3-co-ehloroetylo-, 3-G^chloroheksylo-, 3-metoksy- karbonylometylo-, 3-butoksykarbonylometylo-, 3* -coHmetoksykarbonyloetylo-, 3-cw^propoksykarbony- lo^propylo-, 3-metoksykarbonylo^pentylo-, 3-ca-eto- ksykarbonylopentylo-, 3-co-metoksykarbonylodecy- lo, 3-co^metoksykarbonyloundecylo-, 3-co-alliloksy- karbonylopentylo-, 3-co-morfolinoetylo-, 3-co-morfo- linopropylo-, 3-coHmorfolinoheksylo-, 3-dwumetylo- aminoetylo-, 3-a>-dwuimetyloaminopropyio-, 3-w- -dwuetyloaminopropylo- i 3^dwumetylloamino-2,4- -dwuketo-1,2,3,4Krzterowodoro-sym^triazyno-Il ,2- -va]-benzimidazolu, oraz chlorki, bromki lub jodki trój-n^butylo-, trój-II-rzed-butyle-, trój-III-rzed- -butylo-, trójpentylo-, trój-n-oktylo-, trójcyklo- heksylo- i trójfenyloncyny.Substituted at position 3 14benaimidazolyl-2) - - the teenagers are partly known from the patent specification St. US Am. No. 3,399,212 or may be made according to the method described in this description. ' For example, the following are used in the reaction starting compounds of formulas 2 and 3: sodium salts, potassium, lithium, calcium, magnesium, strontium and barium or trimethyl-, triethyl-, benzyl- dimethyl-, cyclohexyldimethyl-, or dodecyl- trimethylammonium, 3-co-cyjainoethyl-, 3-co-cyja- nopentyl-, 3-co-cyanopentyl-5- or -6-methyl-, 3-ctf-cyariopentyl-5- or -6-butyl-, 3-w-cyano- pentyl-4- or -7-methyl-, 3-cyanoundecyl-, 3-co-chloroethyl-, 3-G ^ chlorohexyl-, 3-methoxy- carbonylmethyl-, 3-butoxycarbonylmethyl-, 3 * -coH-methoxycarbonylethyl-, 3-cn-propoxycarbony- 1-6 propyl-, 3-methoxycarbonyl- pentyl-, 3-ca-etho- xycarbonylpentyl-, 3-co-methoxycarbonyldecy- lo, 3-co-methoxycarbonyloundecyl-, 3-co-allyloxy- carbonylopentyl-, 3-co-morpholinoethyl-, 3-co-morpho- linopropyl-, 3-coHmorpholinohexyl-, 3-dimethyl- aminoethyl-, 3-α> -dimethylaminopropyio-, 3-w- -dimethylaminopropyl- and 3-dimethylamino-2,4- -duketo-1,2,3,4 tetrahydro-sym, triazine-Il, 2- -va] -benzimidazole, and chlorides, bromides or iodides three-n ^ butyl-, three-II-row-butyl-, three-III-row- -butyl-, tripentyl-, tri-n-octyl-, tricyclo- hexyl- and triphenylcyin.
Zwiazki o wzorze 1 otrzymuje sie przez reakcje ewentualnie zawierajacych rozpuszczalnik soli me¬ talu alkalicznego, metalu ziem alkalicznych lub a- monu podstawionego w polozeniu 3 2,4- dwuketo- -1,2,3,4-czterowodO(roHsyim-triazyno-[l,2-a]^benzimi¬ dazolu z halogenkiem trójorganocyny w obojet¬ nym, korzystnie polarnym rozpuszczalniku, np. w dioksanie, acetonitrylu, benizonitrylu lub sulfotlen- ku dwumetylowym albo w mieszaninach rozpusz¬ czalników, w temperaturze 0—150°C, korzystnie 40—60°C.The compounds of formula I are obtained by reactions optionally solvent-containing salts of metals alkaline thallium, alkaline earth metal or a- monon, substituted at position 3, 2,4- -1,2,3,4-tetrahydro (rHsim-triazino- [1,2-a] -benzimim of dazole with the triorganotin halide in neutral with a similar, preferably polar solvent, e.g. dioxane, acetonitrile, benisonitrile or sulfoxide dimethyl or in solvent mixtures at a temperature of 0-150 ° C, preferably 40-60 ° C.
Podstawione w polozeniu 3 1-trójorganostannylo- -2,4^dwuketo-!l,2,3,4-czlterowodorojsym-triazyno- -[l,2-a]-benzimizole sa przewaznie latwiej rozpusz¬ czalne, niz 2,4^dwuketo^czterowodoro-sym-triazy- inóbenzimidazole podstawione w polozeniu 3, a za¬ tem w odpowiednim rozpuszczalniku, np. w chlo¬ roformie lub chlorku metylenu mozna je oddzielic "od, zwiazków wyjsciowych. Po odparowaniu roz¬ puszczalnika pozostaly produikt nalezy oczyscic przez przekrystalizowanie, rozcieranie lub za po¬ moca innych operacji. Niektóre podstawione w po¬ lozeniu 3 l-trójorganostannylo-2,4-dwuketocztero- wodoro-sym^tmazynobeniziimidazole krystalizuja w róznych postaciach i róznia sie wiidmami w pod¬ czerwieni w postaci sprasowanej z bromkiem po¬ tasu, lecz nie róznia sie widmami w podczerwieni w roztworach. Widma w podczerwieni zwiazków o wzorze 1 w roztworach np. w chloroformie, sa w zakresie 1550—ii7,50 om—1 wyraznie rózne od widm podstawionych w polozeniu 3 2,4-dwuketo- czterowodoro-syim-itniaizynobenzijmidazoli np. ukla¬ dem pasm przy 1565, 1585, 1605, 1620 cm-1. Tem¬ peratury topnienia zwiazków stannylowych nie za¬ wsze sa charakterystyczne.Substituted at the position of 3 1-triorganostanyl- -2,4 ^ doublet-! 1,2,3,4-tetrahydro-triazine- - [1,2-a] -benzimizoles are usually easier to dissolve non-2,4 ^ bis-tetrahydro-sym-triazines- the inobenzimidazoles substituted at the 3-position and in a suitable solvent, for example, chlorine form or methylene chloride can separate them "from the starting compounds. After the dissolution has evaporated solvent, the rest of the product should be cleaned by recrystallization, trituration or by polishing the power of other operations. Some substituted with laying 3 l-triorganostannyl-2,4-two-four-four- the hydrogen-symmethazinbenizimidazoles crystallize in different characters and differs in visions in the sub red in a compressed form with bromide tasu, but does not differ in infrared spectra in solutions. Infrared spectra of compounds of formula I in solutions, e.g. in chloroform, sa in the range of 1550 - ii7.50 ohms - 1 clearly different from spectra substituted in position 3 2,4-two-hundred tetrahydro-thyminibenzinobenzimidazoles, e.g. dem bands at 1565, 1585, 1605, 1620 cm-1. Tem¬ the melting point of the stannyl compounds was not present they are all characteristic.
Zwiaizki o wzorze 1, jak juz podano, dzialaja owadobójczo, roztoczobójczo i grzybobójcze Mozna je stosowac z dobrym wynikiem do zwalczania o- wadów o narzadzie gebowym ssacym i gryzacym98703 6 oraz roztoczy i fitopatogennych grzybów. Dzialaja taikze przeciwko szkodnikom sanitarnym i maga¬ zynowym. Skuteczne sa tez w postaci srodków za¬ prawowych i jako fungicydy zbozowe. Ponadto w wyzszych stezeniach roboczych wykazuja dziala¬ nie chwastobójcze przy stosowaniu po wzejscdu ro¬ slin. Dzialanie miikrobosljatyczne umozliwia ich sto¬ sowanie do róznych celów w konserwacji, dezyn¬ fekcji lub apreturach przeciwmikrobowych.The compounds of formula I, as already stated, work insecticidal, acaricidal and fungicidal use them with good results to combat o- wadow with a sucking and biting mouth organ 98703 6 and mites and phytopathogenic fungi. They work taikze against sanitary pests and magazines zinnia. They are also effective in the form of measures legal and as grain fungicides. Moreover, in higher working concentrations do work not herbicidal when used post-emergence slin. The table makes it possible to have a microbosiliatic effect use for various purposes in maintenance, disinfection antimicrobial fections or finishes.
Do owadów o narzadzie gebowym ssacym zwal¬ czanych przez srodki wedlug wynalazku naleza glównie mszyce (Aphidae), np. mszyca brzoskwi¬ niowo-ziemniaczana (Myzus persicae), mszyca trzmielinowo-burakowa (Doralis fabae), mszyca czeremchowo-zbozowa (Rhopalosiphum padr), msizyca grochowa (Macrosiphum pisi), mszyca ziemniaczana smugowana (Macrosiphum solanifo- lii), mszyca porzeczkowa (Gryptomyzus korschelti), mszyca jabloniowo^babkowa (Sappaphis mali), mszyca sliwowo-trzoinowa (Hyalopterus arundinis), mszyca wisniowoHprzytuliowa (Myzus cerasi), po¬ nadto zwalczaja czerwcówate (Coccina), np. tarcz¬ nika oleandirowca (Aspidiotus hederae), Lecanium he&perium, Pseudococcus maritimtis, przylzence (Thysa-noptera), np. Hercinothirips femoralis, plus¬ kwiaki np. plaszczynca burakowego (Piesma qua- drata), Dysdercus intermedius, pluskwe domowa (Cimex lectularius), Rhodnius prolius, Triatoma infestans, dalej piewiki np. Euscelis bilobatus i N>aphotettix bipunctaius.For insects with a sucking organ, slow down Included by the means according to the invention are mainly aphids (Aphidae), eg peach aphids potato beetle (Myzus persicae), aphid beetroot (Doralis fabae), aphid cherry-cereal (Rhopalosiphum padr), pea midge (Macrosiphum pisi), aphid potato streak (Macrosiphum solanifo- lii), currant aphid (Gryptomyzus korschelti), apple-tree aphid (Sappaphis mali), red aphid (Hyalopterus arundinis), huddled-cherry aphid (Myzus cerasi), p moreover, they fight against red beetles (Coccina), for example shields Nica oleander (Aspidiotus hederae), Lecanium he & perium, Pseudococcus maritimtis, przylzence (Thysanoptera), e.g. Hercinothirips femoralis, plus flowers, e.g. beetroot coat (Piesma qua- drata), Dysdercus intermedius, the house bug (Cimex lectularius), Rhodnius prolius, Triatoma infestans, then chants, e.g. Euscelis bilobatus and N> aphotettix bipunctaius.
Do owadów o narzadzie gebowym gryzacym zwalczanych przez srodki wedlug wynalazku na¬ leza przede wszystkim gasienice motyli (Lepidop- tera), takich jak tantnis krzyzowiaczek (Plutella maculipennis), brudnica nieparka (Lymantris dis- par), kuprówka-rudnica (Euproctis chrysorrhoea), przadka pierscienica (Melacosoma neustria), po¬ nadto pietnówfca kapustówfka (Mamestra brassicae), zbozówka rolnica (Agrotis segetum), bielinek ka- puistnik (Pieiris brassicae), piejdzik przedzimek (Cheimatobia bruma-ta), zwójka zieloneczka (Tor- trix viridana), Laphygma frugiperda, Prodenia li- tura, dalej namiotnik owocowy, (Hyponomeuta pa- della), molik maczny (Ephestia kiihniella) i barciak . wiekszy (Galleria mellonella). ' Ponadto do owadów o narzadzie gebowym gry¬ zacym zwalczanych przez srodki wedlug wynalazku naleza chrzaszcze (Coleoptera), np. wolek zbozowy (Sitophilus ^ granarius = Calandra granaria), ston¬ ka ziemniaczana (Deptinotarsa dscemlineata), ka- ludmca zielonka (Gastrophysa viridula), zaczka chrzanówka (Phaedon cochJtariafck slodyszek rze¬ pakowy (Meligethes aeneus), kistnik maHoitóL (By- turus tomentosus), sfcrakowiec fasolowy (Bruchi- dius = Acanthosceiides obtectus), Dermestes fris- chi, skórek zbozowiec (Trogoderma granarium), trojszyk gryzacy (Tribolium castaneum), wolek ku¬ kurydziany (Calandra lub Sitophilus zeamais), zy- wiak chlebowiec (Stegobium paniceum), macznik mlynarek (Tenebrlio molitor), spichrzel surynamski (Oryzaephilus surinamensis), oraz rodzaje zyjace w glebie, np. drutowce (Agriotes spec.), chrabasz¬ cze majowe (Melolontha melolontha), karaluchy, np. prusak (Blatella germanica), przybyszka'ame¬ rykanska (Periplarieta acmeiricana), Deucophaea lub Rhyparobia maderae, karaczan wschodni (Blatta orientalis), Blaberus giganteus, Blaberus fuscus, Henschoutedenia flexivitta, dalej róznoskrzydie, np. swierszcz domowy (Gryllus domesticus), termi- ty np. Reticuliermes flavdpes i blonoskrzydle, np. mrówki, przykladowo hurtnica czarna (Lasius ni- ger).For biting insects to be combated by the agents according to the invention mainly butterfly caterpillars (Lepidop- tera), such as the Cross Tantnis (Plutella maculipennis), gypsy moth (Lymantris dis- par), tuft-rudnica (Euproctis chrysorrhoea), spider ring (Melacosoma neustria), po too much pietnówfca cabbage soup (Mamestra brassicae), agricultural cereal (Agrotis segetum), the parchment (Pieiris brassicae), early primrose (Cheimatobia bruma-ta), green leaf roll (Tor- trix viridana), Laphygma frugiperda, Prodenia li- aurora, then a fruit tent, (Hyponomeuta pa- della), flour molik (Ephestia kiihniella) and mallow . larger (Galleria mellonella). ' Moreover, for insects with a mouth organ by the agents of the invention These include beetles (Coleoptera), e.g. corn veal (Sitophilus ^ granarius = Calandra granaria), ston potato ka (Deptinotarsa dscemlineata), ka- ludmca green forage (Gastrophysa viridula), wait horseradish (Phaedon cochJtariafck slodyszek rze¬ packet (Meligethes aeneus), kistnik maHoitóL (By- turus tomentosus), bean spider (Bruchi- dius = Acanthosceiides obtectus), Dermestes fris- chi, skins of a corn (Trogoderma granarium), chewing trout (Tribolium castaneum), chicken wolf corn (Calandra or Sitophilus zeamais), zy- breadfruit (Stegobium paniceum), macznik mill (Tenebrlio molitor), Suriname Granary (Oryzaephilus surinamensis), and species of living creatures in soil, e.g. wireworms (Agriotes spec.), horseradish June May (Melolontha melolontha), cockroaches, e.g. German Prussian (Blatella germanica), newcomer'ame¬ rykanska (Periplarieta acmeiricana), Deucophaea or Rhyparobia maderae, Eastern cockroach (Blatta orientalis), Blaberus giganteus, Blaberus fuscus, Henschoutedenia flexivitta, hereinafter various wings, e.g. house cricket (Gryllus domesticus), termi- you, e.g., Reticuliermes flavdpes, and moths, e.g. ants, for example black wholesaler (Lasius ger).
Z dwuskrzydlych zwalczaja glównie muchy, np. wywilzyne karlówke (Drosophila melanogaster), owocanke poludniówke (Ceratdtis capitaita), muche domowa (Musca domesitica), muche pokojowa (Fan- nia canicularisK Phórmia regina, plujke rudoglo- wa (Callfliphora erythrocephala) oraz bolimuszke kleparke (Stomoxys calcitrans), dalej dlugoezUl- kie, jak komary, np. Aedes aegypti, Culex pipiens m i Anopheles stephensi. ( Do roztoczy (Acari) zwalczanych przez srodki wedlug wynalazku naleza zwlaszcza przejdziorko- wate (Tetranychidae), np. przedziorek Chmielowiec (Tetranychus telarius = Tetranychus althaeae lub Tetranychus urticae) i przedziorek owocowiec (Pa- ratetranychus pdlosus — Panonychus umi), szpe- cielowate, np. szpeciel porzeczkowy (Eriophyes ri- bis), roztocza róznopazurkowate, np. Hemitarso- nemus latus i roztocz truskawkowy (Tarsonemus pallidus) i kleszcze, np. Orni/thodorus moubata.From two-winged ones they mainly fight flies, e.g. displaced dwarf (Drosophila melanogaster), midwort fruit (Ceratdtis capitaita), muche house muche (Musca domesitica), room muche (Fan- nia canicularisK Phórmia regina, redhead spit wa (Callfliphora erythrocephala) and bolimuszke hacker (Stomoxys calcitrans), continue for long as mosquitoes, e.g. Aedes aegypti, Culex pipiens m and Anopheles stephensi. ( For mites (Acari) combated by measures according to the invention, there is in particular wate (Tetranyidae), e.g. the front hole of Chmielowiec (Tetranyus telarius = Tetranyus althaeae or Tetranyus urticae) and the fruit front (Pa- ratetrańus pdlosus - Panonychuskich), espe- calves, e.g. black currant (Eriophyes ri- bis), multitaw mites, e.g. Hemitarso- nemus latus and the strawberry mite (Tarsonemus pallidus) and ticks, e.g. Orni / thodorus moubata.
W pirzypadku stosowania w dziedzinie higieny i przechowalnictwa, zwlaszcza przeciwko muchom i komarom, srodki wedlug wynalazku wykazuja do¬ skonale dzialanie pozostalosciowe na drewnie i glinie i dobra odpornosc na alkalia na uwapnio- nyeh podlozach.When used in the field of hygiene and containment, especially against flies and against mosquitoes, the agents according to the invention show well excellent residual action on wood i clay and good alkali resistance to calcium nyeh substrates.
Substancje czynne mozna stosowac do zwalcza¬ nia szkodliwych Acrchimycetes, Phycomycetes, As- comycetes, Basidiomycetes oraz Fungi imperfecti.The active substances can be used to combat harmful Acrchimycetes, Phycomycetes, As- comycetes, Basidiomycetes and Fungi imperfecti.
Subsftancje czynne srodka wedlug wynalazku wy¬ kazuja dzialanie zarówno zapobiegawcze, jak i lecznicze i systemdczne. Mozna je ^zatem stosowac nie tylko profilaktycznie, lecz równiez po wysta¬ pieniu objawów infekcji. Mozna równiez zwal¬ czac grzybice rozwijajace sie w roslinie. Stosuje sie je do zwalczania chorób roslin uprawnych wy¬ wolanych grzybami lub bakteriami, takimi jak ro¬ dzaje Venturia (np. parch jabloniowy, gruszowy), Botryfcis cinerea, Solerotinia selerotiiorum, rodzaje Alternaria, rodzaje Cercospora, Myeospharella musicola, Phytophtora infestans, .Plasmopara vi- ticola, rodzaje Erysiiphe, PodosphaeTa, leucofricha.The active subsidies of the agent according to the invention are they are both preventive and medicinal and systemic. So they can be used not only prophylactically, but also after occurrence foaming symptoms of infection. You can also fire hide mycoses developing in the plant. Applies they are used to combat diseases of cultivated plants foul fungi or bacteria, such as ro Venturia trees (e.g. apple and pear scab), Botryfcis cinerea, Solerotinia selerotiiorum, genera Alternaria, genera Cercospora, Myeospharella musicola, Phytophtora infestans, .Plasmopara vi- ticola, genera Erysiiphe, PodosphaeTa, leucofricha.
Duze znaczenie praktyczne jak równiez wysoka skutecznosc maja substancje czynne w przypadku stosowania w postaci srodków do zaprawiania na¬ sion i srodków do traktowania gleby sluzacych do zwalczania fitopatogennych grzybów zwiazanych z nasionami lub znajdujacych sie w glebie, wywolu¬ jacych u roslin uprawnych choroby kielków, zgni¬ lizne koraiaai^ tracheomylkozy, choroby lodygi, zdzbla, lisci, kwiatów, owoców lub nasion, takich jak Tilletia caries, HftLminthosporium gramineum, Fusarium nivale, Fusariuea culmorum, Rhizoctonia solana, Phialophora cineresc«ns, Verticiilium albo- atrum, Fusarium dianthi, Fusariujm cubense, Fusa¬ rium oxysporuim, Fusarium solani, acflerotinia scle- rotiorum, ThdelaviO|psis basicola i Phytophtora ca- ctorum. * Mozns^ równiez zwalczac bakterie wywolujace 40 45 50 55 607 choroby roslin takie jak Xanthomonas oryzae, Xanthomonas vesicatoria, Xanthomonas citri, Pseudomonas lachrymans, Pseudomonas morspho- norum, Pseudomonas solani i rodzaje Erwinia.High practical importance as well as high the effectiveness of the active substances in the case to be used as a dressing agent seeds and soil treatment agents used for combating phytopathogenic fungi associated with by seeds or in the soil, grow diseases of sprouts in crops, rotted lizne koraiaai ^ tracheomyloses, stem diseases, sticks, leaves, flowers, fruit or seeds such as like Tilletia caries, HftLminthosporium gramineum, Fusarium nivale, Fusariuea culmorum, Rhizoctonia solana, Phialophora cineresc «ns, Verticiilium or- atrum, Fusarium dianthi, Fusariujm cubense, Fusa¬ rium oxysporuim, Fusarium solani, acflerotinia scle- rotiorum, ThdelaviO | psis basicola and Phytophtora ca- ctorum. * They can also fight causing bacteria 40 45 50 55 607 plant diseases such as Xanthomonas oryzae, Xanthomonas vesicatoria, Xanthomonas citri, Pseudomonas lachrymans, Pseudomonas morspho norum, Pseudomonas solani, and Erwinia genera.
Substancje czynne mozna przeprowadzac w zwy- 5 kle zestawy w postaci roztworów, emulsji, zawie¬ sin, proszków, past i granulatów. Otrzymuje sie je w znany sposób, np. przez zmieszanie substan¬ cji czynnych z rozcienczalnikami, to jest ciekly¬ mi rozpuszczalnikami, skroplonymi pod cisnieniem 10 gazami i/lub stalymi nosnikami, ewentualnie stosujac substancje powierzchniowo czynne takie jak. emulgatory i/lub dyspergatory i/lub srodki , pianotwórcze.The active substances can be converted into the usual 5 glue kits in the form of solutions, emulsions, suspensions sin, powders, pastes and granules. I get them in a known manner, for example by mixing the substances together active substances with diluents, that is, liquid m and solvents liquefied under pressure 10 gases and / or solid carriers, optionally using surfactants such how. emulsifiers and / or dispersants and / or agents, foaming.
W przypadku stoisowania wody jako rozcienczal¬ nika mozna stosowac np. rozpuszczalniki organicz¬ ne sluzace jako rozpuszczalniki pomocnicze. Jako ciekle rozpuszczalniki mozna stosowac zasadniczo zwiazki aromatyczne np. ksylen, toluen, benzen lub alkilonaftaleny, chlorowane zwiazki aroma¬ tyczne lub chlorowane* weglowodory alifatyczne, takie jak chlorobenzeny, chloroetyleny lub chlorek metylenu, weglowodory alifatyczne, takie jak cy¬ kloheksan lub parafiny np. frakcje ropy naftowej, alkohole, takie jak butanol lub glikol oraz ich e- tery i estry, ketony, takie jak aceton, metyloetylo- keton, metyloizobutyloketon lub cykloheksanon, rozpuszczalniki o duzej polarnosci, takie jak dwu- metyloformamid i* sulfotlenek dwumetylowy, oraz wode. Jako skroplone gazowe rozcienczalniki lub nosniki stosuje sie ciecze, które w normalnej tem¬ peraturze i pod normalnym cisnieniem sa gazami, np. gazy aerozolotwórcze, takie jak chlorowcowe- glowodory np. freon. Jako stale nosniki stosuje sie naturalne maczki mineralne, takie jak kaoliny, tlenki glinu, talk, kreda, kwarc, atapuligit, mont- moryloriit lub ziemia okrzemkowa i syntetyczne maczki nieorganiczne, takie jak kwas krzemowy o wysokim -stopniu rozdrobnienia, tlenek glinu i krzemiany. Jako emulgatory i/lub srodki piano¬ twórcze stosuje sie emulgatory niejonotwórcze i anionowe, takie jak estry politlenku etylenu i kwasów tluszczowych, etery politlenku etylenu i alkoholi tluszczowych, np. etery alkiloarylopoli- gliikolowe, alkilosulfoniany, siarczany alkilowe, a- rylosulfoniany oraz hydrolizaty^ bialka. Jako srod¬ ki dyspergujace stosuje sie np. lignine, lugi po¬ siarczynowe i metyloceluilaze.In the case of using water as a diluent For example, organic solvents can be used ne serving as auxiliary solvents. As liquid solvents can be used in principle aromatic compounds, e.g. xylene, toluene, benzene or alkyl naphthalenes, chlorinated aromatics tic or chlorinated * aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or chloride methylene; aliphatic hydrocarbons such as cy clohexane or paraffins, e.g. crude oil fractions, alcohols such as butanol or glycol and their e- terers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, high polarity solvents such as bi- methylformamide and * dimethyl sulfoxide, and water. As liquefied gaseous diluents or the carriers use liquids which, at normal temperature, at normal pressure and under normal pressure they are gases, e.g. aerosol propellants such as halogenated hydrocarbons, e.g. freon. As permanent carriers are used natural mineral meals, such as kaolins, aluminum oxides, talc, chalk, quartz, attapuligite, mont- moryloriite or diatomaceous earth and synthetic inorganic powders such as silicic acid o high-fineness, aluminum oxide and silicates. As emulsifiers and / or foam agents creative, non-ionic emulsifiers and anionic such as polyethylene oxide esters and fatty acids, polyethylene oxide ethers and fatty alcohols, e.g. alkylaryl polyol ethers glycol, alkyl sulfonates, alkyl sulfates, a- rylsulfonates and protein hydrolysates. As Wednesday Dispersants are used, for example, lignin, lingons sulfite and methylcellilase.
Preparaty substancji czynnych srodka wedlug 50 wynalazku moga -zawierac domieszki innych, zna¬ nych substancji czynnych. Preparaty zawieraja przewaznie 0,1.—95% wagowych, korzystnie 0,5— 90% wagowych substancji czynnej.Preparations of the active substances of the agent according to 50 the invention may contain admixtures of others, e.g. active substances. Preparations include mostly 0.1-95% by weight, preferably 0.5- 90% by weight of active ingredient.
Substancje czynne mozna stosowac same, w po- 55 staci koncentratów lub przygotowanych z nich pre¬ paratów roboczych, takich jak gotowe do uzycia roztwory, emulsje, pianki, zawiesiny, proszki, pa¬ sty, proszki rozpuszczalne, proszki do opylania i granulaty. 60 Srodki stosuje sie w znany sposób, np. przez o- pryskiwanie, opryskiwanie mglawicowe, opylanie mglawicowe, rozsiewanie, odymianie, gazowanie, podlewanie, zaprawianie lub inkrustowanie.The active substances can be used alone, over 55 concentrates or pre-prepared from them workbenches, such as ready-to-use solutions, emulsions, foams, suspensions, powders, powders sty, soluble powders, dusting powders and granulates. 60 The measures are used in a known manner, e.g. by spraying, nebular spraying, dusting nebular, spreading, fumigation, gassing, watering, dressing or encrusting.
Stezenie substancji czynnych w preiparatach ro- 65 8 bocznych moze wahac sie w szerokich granicach.Concentration of active substances in ro-65 pre-instruments 8 the lateral sides can vary widely.
Na ogól stezenie wynosi 0,00011—10%, korzystnie 0,01^1%.In general the concentration is 0.00011-10%, preferably 0.01 ^ 1%.
Substancje czynne mozna stosowac z dobrym wynikiem sposobem Ultra-Low-Volume (ULV), w którym mozna nanosic preparaty zawierajace do 95% substancji czynnej lub nawet sama 100% sub¬ stancje czynna. W przypadku stosowania do ob¬ róbki nasion uzywa sie na ogól 0,1—10 g/kg, ko¬ rzystnie 0,5—5 g/kg nasion. Do obróbki gleby sto¬ suje sie 1^500 g, korzystnie 10—200 g substancji czynnej na m3 gleby.The active substances can be used with good the result by the Ultra-Low-Volume (ULV) method, v which you can apply preparations containing to 95% of the active ingredient or even 100% of the active ingredient alone the station is open. When used for the object The seed products are generally used from 0.1-10 g / kg, co preferably 0.5-5 g / kg of seeds. For the treatment of soil 1 to 500 g, preferably 10 to 200 g of substance are used active per m3 of soil.
Nizej podane przyklady sluza do potwierdzenia skutecznosci dzialania substancji czynnych srodka, przy czym spektrum dzialania substancji czynnych nie ogranicza sie do wymienionych przykladów.The examples below are for confirmation the effectiveness of the active substances of the agent, the spectrum of action of the active substances not limited to the examples mentioned.
Przyklad I. " Test LT10o dla dwuskrzydlych.Example I. "LT10o test for two-wingers.
Testowany owad: Musca domestica. Rozpuszczal¬ nik: aceton.Insect tested: Musca domestica. Solvent nick: acetone.
Rozpuszcza sie 2 czesci wagowe substancji czyn¬ nej w 1000 czesciach objetosciowych rozpuszczalni¬ ka. Tak otrzymany roztwór rozciencza sie tym sa¬ mym rozpuszczalnikiem do osiagniecia mniejszego zadanego stezenia.2 parts by weight of the active ingredient are dissolved in 1000 parts by volume of solvent ka. The solution thus obtained is diluted with the same my solvent to achieve less the desired concentration.
Do naczynka Petriego wprowadza sie pipetka 2,5 ml roztworu substancji czynnej. Na dnie na¬ czynka znajduje sie bibula filtracyjna o srednicy okolo 9,5 cm. Naczynko pozostawia sie otwarte do calkowitego ulotnienia sie rozpuszczalnika. W za¬ leznosci od stezenia roztworu substancji czynnej ilosc substancji czynnej przypadajacej na I m2 bibuly jest rózna. Nastepnie do naczynka wprowa¬ dza sie okolo 25 testowanych owadów i naczynko przykrywa wieczkiem szklanym.A pipette is inserted into the Petri dish 2.5 ml of active substance solution. At the bottom of the day There is a filter paper with a diameter about 9.5 cm. The dish is left open until complete evaporation of the solvent. In za¬ dependence on the concentration of the active substance solution amount of active substance per 1 m2 the papers is different. Then introduce into the dish There are about 25 tested insects and a dish covered with a glass lid.
Stan zwierzat bada sie na biezaco. Ustala sie czas# uplywajacy do wystapienia 100% smiertelno¬ sci.The condition of the animals is monitored on an ongoing basis. It settles time until 100% mortality occurs sci.
W tablicy ,1 podaje sie testowane owady, sub¬ stancje czynne, ich stezenia oraz czas uplywajacy do wystapienia 100% smiertelnosci.In Table 1 the insects tested are given, sub active states, their concentrations and elapsed time until 100% mortality occurs.
Pi r z yj k l a d II. Test LT10o dla dwuskrzydlych.Pi r z yj k l a d II. LT10o test for two-wingers.
Testowany owad: Aedes aegypti. Rozpuszczalnik: aceton.Insect tested: Aedes aegypti. Solvent: acetone.
Rozpuszcza sie 2 czesci wagowe substancji czyn¬ nej w 1000 czesciach objetosciowych rozpuszczal¬ nika. Tak otrzymany roztwór rozciencza sie tym samym rozpuszczalnikiem do osiagniecia mniejsze¬ go zadanego stezenia.2 parts by weight of the active ingredient are dissolved in 1000 parts by volume of solvents nika. The solution thus obtained is diluted with this with the solvent alone to achieve less the desired concentration.
Do naczynka Petriego wprowadza sie pipetka 2,5 ml roztworu substancji czynnej.. Na dnie na¬ czynka znajduje sie bibula filtracyjna o srednicy okolo 9,5 cm. Naczynko pozostawia sie otwarte do calkowitego ulotnienia sie rozjiuszczalndJka. W za¬ leznosci od stezenia roztworu substancji czynnej ilosc substancja czynnej przypadajaca na 1 rti2 bi^ buly jest zupelnie rózna. Nastepnie do naczynka wprowadza sie okolo 25 testowanych owadów i na¬ czynko przykrywa wieczkiem szklanym.A pipette is inserted into the Petri dish 2.5 ml of active ingredient solution .. At the bottom of the There is a filter paper with a diameter about 9.5 cm. The dish is left open until the complete volatilization would dissolve. In za¬ dependence on the concentration of the active substance solution amount of active substance per 1 rt12 bi ^ buly is completely different. Then into the dish about 25 tested insects are introduced and na¬ The box is covered with a glass lid.
Stan zwierzat bada sie na biezaco. Ustala sie czas uplywajacy do wystapienia 100% smiertelno¬ sci.The condition of the animals is monitored on an ongoing basis. It settles time elapsing until 100% mortality occurs sci.
W tablicy 2 podaje sie testowane owady, sub¬ stancje czynne, ich stezenia oraz czas uplywajacy do wystapienia 100% smiertelnosci.JSM3 Test LT10o dla Tablica ii dwusk.rzydlych stica) (Musca donie- Substancja 'czynna 1 Znane: zwiazek o wzo¬ rze 4 zwiazek o wzo¬ rze 5 • Wedlug wyna¬ lazku: zwiazek o wzo¬ rze 6 izwiaizek o wzo- . irze 7 zwiazek o wzo¬ rze 8 zwiazek o wzo¬ rze 9 zwiazek o wzo¬ rze 10 zwiazek o wzo¬ rze 11 Stezenie sub¬ stancji czyn¬ nej w roztwo¬ rze w °/o 2 0,2 0,2 0,2 0,02 0,2 0,02 0,2 . 0,02 0,2 0,02 i LT10o a 8h = 90o/q 8h =, 90°/o 130' 6h 170' 61* =, 90fVo 120' 70' eh = ao°/o 50' 160' 0,2 85' 1 Tablica 2 Test LTjoo dla dwuskrzydlych (Aedes aegypti) Substancja czynna Znane: zwiazek o wzo¬ rze 4 zwiazek o wzo¬ rze 5 Wedlug wyna¬ lazku: zwiazek o wzo¬ rze 6 zwiazek o wzo¬ rze 7 zwiazek o wzo¬ rze 8 zwiazek o wzo¬ rze 9 . zwiazek o wzo¬ rze 10 zwiazek o wzo¬ rze 11 Stezenie sub¬ stancji czyn¬ nej w roztwo¬ rze w °/o 0,2 0,2 0,2 0,02 0,2 0,02 0,2 0,02 0,2 0,02 0,2 0,02 0,2 0,02 LT100 3h=,0°/o 3h = 0*/o • 60' 60' 60' 3h = £,0O/O 60' 3h =, 50Vo 60' 120' 60' 60' 60' 120' Przyklad III. Testowanie Tetranychus (od¬ porny).Table 2 lists the insects tested, sub active states, their concentrations and elapsed time until the occurrence of 100% mortality. JSM3 LT10o test for Table ii double winged stica) (Musca don- Substance 'open 1 Known: relationship about pattern rze 4 relationship about pattern at 5 • According to the rental lazku: relationship about pattern rze 6 izwiaizek with wzo-. irze 7 relationship about pattern rze 8 relationship about pattern rze 9 relationship about pattern rze 10 relationship about pattern rze 11 Concentration of sub of activities in solution rze w ° / o 2 0.2 0.2 0.2 0.02 0.2 0.02 0.2 . 0.02 0.2 0.02 and LT10o and 8h = 90o / q 8h = .90% 130 ' 6h 170 ' 61 * = .90fVo 120 ' 70 ' eh = ao ° / o 50 ' 160 ' 0.2 85 '1 Table 2 LTjoo test for two-wingers (Aedes aegypti) Substance open Known: relationship about pattern rze 4 relationship about pattern rze 5 According to the rental lazku: relationship about pattern rze 6 relationship about pattern rze 7 relationship about pattern rze 8 relationship about pattern rze 9 . relationship about pattern rze 10 relationship about pattern rze 11 Concentration of sub of activities in solution rze w ° / o 0.2 0.2 0.2 0.02 0.2 0.02 0.2 0.02 0.2 0.02 0.2 0.02 0.2 0.02 LT100 3h = .0% 3h = 0 * / o • 60 ' 60 ' 60 ' 3h = £ .0O / O 60 ' 3h = .50Vo 60 ' 120 ' 60 ' 60 ' 60 ' 120 ' Example III. Testing Tetranyus (od¬ porny).
Rozpuszczalnik: 3 czesci wagowe dwumetylofor- mamidu; emulgator: 1 czesc wagowa eteru alkilo- arylopoliglikolowego. 40 50 55 60 65 ió W celu otrzymania odpowiedniego preparatu substancji czynnej miesza sie 1 czesc substancji czynnej z podana iloscia rozpuszczalnika i podana iloscia emulgatora, po czym koncentrat rozciencza sie woda dó zadanego stezenia. Otrzymanym pre¬ paratem substancji czynnej opryskuje sie mglawi¬ cowo do orosienia siewki fasoli (Phaseolus vulga- ris) o wysokosci okolo 10—30 cm. Siewki te sa silnie porazone wszystkimi stadiami rozwojowymi przedziorka chmielowca (TetranyChus urticae). Po uplywie podanego czasu ustala sie skutecznosc preparatu substancji czynnej liczac martwe zwie¬ rzeta. Tak otrzymana smiertelnosc podaje sie w */o, przy czym 100% oznacza, ze wszystkie prze- dziorki zostaly zabite, a 0% oznacza, ze zaden przedziorek nie zostal zabity.Solvent: 3 parts by weight dimethylform mamidu; emulsifier: 1 part by weight of an alkyl ether aryl polyglycol. 40 50 55 60 65 ió In order to obtain the appropriate preparation the active substance is mixed with 1 part of the substance active with the stated amount of solvent and stated amount of emulsifier, then the concentrate is diluted the water goes to the desired concentration. Received pre¬ spray of active substance is sprayed with mist bean seedlings (Phaseolus vulga- ris) about 10-30 cm high. These seedlings are strongly affected by all stages of development hops moth (TetranyChus urticae). After after this time, the effectiveness is determined of the preparation of active substance, counting dead animals a ripple. The mortality thus obtained is given in v * / o, where 100% means that all bells have been killed and 0% means none the hole was not killed.
W tablicy 3 podaje sie substancje czynne, ste¬ zenia substancji czynnych, czasy obserwacji oraz uzyskane wyniki.Table 3 lists the active ingredients, ste the active substances, observation times and obtained results.
Tablica 3 • Roztocza — szkodniki roslin Testowanie Tetranychus Substancja czynna | 1 zwiazek o wzo¬ rze 12 (znany) zwiazek o wzo¬ rze 7 zwiazek o wzo¬ rze 6 zwiazek o wzo¬ rze 10 zwiazek o wzo¬ rze 13 zwiazek o wzo¬ rze 14 zwiazek o wzo¬ rze 11 zwiazek o wzo¬ rze 8 zwiazek o wzo¬ rze 15 zwiazek o wzo¬ rze 16 zwiazek o wzo¬ rze 17 zwiazek o wzo¬ rze 18 zwiazek o wzo¬ rze 19 zwiazek o wzo¬ rze 20 zwiazek o wzo¬ rze 21 Stezenie sub¬ stancji czyn¬ nej w °/o 0,1 0,01 0,1 0,01 0,1 0,01 0,1 0,01 0,1 0,01 0,1 0,01, 0,1 0,01 0,1 0,01 0,1 0,01 0,1 0,01 0,1 0,01 0,1 0,01 0,1 0,01 0,1 0,01 0,1 0,01 Smiertelnosc w °/o po uply¬ wie 2 dni 3 95 0 100 100 100 llOO 100 . 95 100 98 100 100 100 98 100 100 aoo iao 100 98 100 98 100 100 100 98 100 99 100 100 Przyklad IV. Testowanie Phytophtora midory) dzialanie zapobiegawcze.Table 3 • Mites - plant pests Testing Tetranyus Substance open | 1 relationship about pattern age 12 (known) relationship about pattern rze 7 relationship about pattern rze 6 relationship about pattern rze 10 relationship about pattern on 13 relationship about pattern on 14 relationship about pattern rze 11 relationship about pattern rze 8 relationship about pattern sep 15 relationship about pattern on 16 relationship about pattern on 17 relationship about pattern on 18 relationship about pattern on 19 relationship about pattern on 20 relationship about pattern on 21 Concentration of sub of activities nej in ° / o 0.1 0.01 0.1 0.01 0.1 0.01 0.1 0.01 0.1 0.01 0.1 0.01, 0.1 0.01 0.1 0.01 0.1 0.01 0.1 0.01 0.1 0.01 0.1 0.01 0.1 0.01 0.1 0.01 0.1 0.01 Mortality w% after expired knows 2 days 3 95 0 100 100 100 lOOO 100 . 95 100 98 100 100 100 98 100 100 aoo iao 100 98 100 98 100 100 100 98 100 99 100 100 Example IV. Phytophtor testing midory) preventive action.
Rozpuszczalnik: 4,7 czesci wagowe acetonu; (po- e-ii d&703 muigaitor: 0,3 czesci wagowej eteru alkiloarylo- -poligilikolowego; woda: 95,0 czesci wagowych.Solvent: 4.7 parts by weight of acetone; (after- e-ii d & 703 muigaitor: 0.3 parts by weight of alkylaryl ether -polyglycol; water: 95.0 parts by weight.
W celu otrzymania cieczy do opryskiwania o za¬ danym stezeniu substancji czynnej miesza sie po¬ trzebna ilosc substancji czynnej z podana iloscia rozpuszczalnika i koncentrat rozciencza sie poda¬ na iloscia wody zawierajaca wymienione dodatki.In order to obtain a spraying liquid of at a given concentration of active ingredient, mixed the required amount of active ingredient with the stated amount solvent and the concentrate is diluted with administration with a quantity of water containing the listed additives.
Otrzymana ciecza do opryskiwania opryskusje sie do orosienia mlode pomidory o 2—i lisciach asy- milacyjnych. Rosliny pozostawia sie w szklarni w ciagu 24 godzin w temperaturze 20°C i wzglednej wilgotnosci powietrza wynoszacej 70%. Nastepnie pomidory inokuluje sie wodna zawiesina zarodni¬ ków Phytophtora infestans. Rosliny wprowadza sie do komory wilgotnej o wilgotnosci powietrza wy¬ noszacej 100% i temperaturze 18-^20°C.The resulting spray liquid will spray on for dripping wet young tomatoes with 2-leaves and asy- milestones. Plants are left in the greenhouse in within 24 hours at 20 ° C and relative temperature air humidity of 70%. Next tomatoes are inoculated with an aqueous spore suspension Phytophtora infestans. The plants are moving in to a humid chamber with an air humidity off at 100% and at a temperature of 18- ^ 20 ° C.
Po uplywie 5 dni ustala sie porazenie pomido¬ rów. Otrzymane wartosci przelicza sie na poraze¬ nie w %, przy czym 0% oznacza brak porazenia, a 100% oznacza, ze rosliny ulegly calkowicie in¬ fekcji.After 5 days, the tomato paralysis is determined trench. The values obtained are converted into paralysis not in%, where 0% means no electric shock, and 100% means that the plants have completely changed fections.
W tablicy 4 podaje sie substancje czynne, steze¬ nia substancji czynnych oraz uzyskane wyniki.Table 4 lists the active substances and concentrations of active substances and the results obtained.
Tablica 4 Testowanie Phytophtora (pomidory) dzialanie za¬ pobiegawcze Substancja czynna I zwiazek o wzo¬ rze 4 (znany) zwiazek o wzo¬ rze 10 Porazenie w % przy stezeniu substancji czynnej 0„'0062% 1A0 0,00156% .11 Przyklad V. Testowanie Fusicladium (parch jabloniowy) dzialanie zapobiegawcze.Table 4 Testing Phytophtora (tomatoes) action activ provisional Substance open And a relationship about the pattern age 4 (known) relationship about pattern rze 10 Electrocution in% at concentration active substance 0 "0062% 1A0 0.00156% .11 Example V. Testing of Fusicladium (scab apple tree) preventive action.
Rozpuszczalnik: 4,7 czesci wagowych acetonu; emulgator: 0,3 czesci wagowej eteru alkiloarylo- poliglikolowego; woda: 95,0 czesci wagowych.Solvent: 4.7 parts by weight of acetone; emulsifier: 0.3 parts by weight of alkylaryl ether polyglycol; water: 95.0 parts by weight.
*W celu otrzymania cieczy do opryskiwania o zadanym sttezeniu substancji czynnej miesza sie potrzebna ilosc substancji czynnej z podana ilo¬ scia rozpuszczalnika, po czym koncentrat rozcien¬ cza sie* podana iloscia wody zawierajacej podane dodatki, (ftrzymana ciecza do opryskiwania opry¬ skuje sie do orosienia mlode siewki jabloni w sta¬ dium "4—6 lisci. Rosliny pozostawia sie w szklarni w ciagu 24 godzin w temperaturze 2fi°C przy wzglednej wilgotnosci powietrza wynoszacej 70%.* To obtain a spray liquid for o The desired active ingredient concentration is mixed the required amount of active ingredient with the stated amount After the solvent was poured on, the concentrate was diluted It may be * given amount of water containing given additives, (retained spray liquor sprayed young apple seedlings are springing up to reflux dium "4-6 leaves. Plants are left in the greenhouse within 24 hours at 2 ° C at relative air humidity of 70%.
Nastepnie inokuluje sie je wodna zawiesina zarod¬ ników konidialnych parcha jabloniowego (Fusicla¬ dium dendriticum Fuck) i inkubuje w ciagu 18 godzin w komorze wilgotnej w temperaturze 18— °C i 100% wzglednej wilgotnosci powietrza.They are then inoculated with an aqueous seed suspension conidia of apple scab (Fusicla¬ dium dendriticum Fuck) and incubates for 18 hours in a humid chamber at a temperature of 18- ° C and 100% relative air humidity.
Roslin^ ponownie wstawia do szklarni na okres ,14 dni. Po uplywie 15 dni po inokulacji okresla sie porazenie siewdek w stosunku procentowymi do porazenia inokulowanych, lecz nie leczonych sie- wiek kontrolnych, przy czym 0% oznacza brak porazenia, a 100% oznacza, ze porazenie jest takie, jak u roslin kontrolnych. 50 55 60 IZ W tablicy 5 podaje sie substancje czynne, ste¬ zenia substancji czynnych oraz uzyskane wyniki.The plant ^ puts it back in the greenhouse for a period ,14 days. He determines 15 days after inoculation infection of seedlings in percentage to paralysis of inoculated, but not treated, age of the controls, with 0% being absent shock, and 100% means that the shock is such as for control plants. 50 55 60 IZ Table 5 lists the active ingredients, ste the active substances and the results obtained.
Tablica 5 Testowanie Fusicladium (jablon) dzialanie zapobie¬ gawcze Substancja czynna zwiazek o wzo¬ rze 4 (znany) zwiazek o wzo¬ rze 10 zwiazek o wzo¬ rze 11 zwiazek o wzo- 1 rze 6 | zwiazek o wzo¬ rze 8 zwiazek o wzo¬ rze 13 Porazenie w % przy stezeniu substancji czynnej 0,0062% 72 . — - — — — ¦ ^~~ 0,0025% — 4 1 57 0 . 22 , 3(2.Table 5 Testing the Fusicladium (apple tree) preventive action warning Substance open relationship about pattern age 4 (known) relationship about pattern rze 10 relationship about pattern rze 11 relationship about the formula 1 st 6 | relationship about pattern rze 8 relationship about pattern on 13 Electrocution in% at concentration active substance 0.0062% 72. - - - - - ¦ ^ ~~ 0.0025% - 4 1 57 0 . 22 , 3 (2.
Przyklad VI. Testowanie rozwoju grzybni.Example VI. Testing mycelium development.
Stosowana pozywka: 20 czesci wagowych agar- -agar, 200 czesci wagowych wyciagu ziemniacza¬ nego, 5 czesci wagowych slodu, 15 czesci wagowych dekstrozy, 5 czesci wagowych peptonu, 2 czesci wagowe Na2HP04, 0,3 czesci wagowych Ca(No3)2 na 1000 cm3 wody.Nutrient used: 20 parts by weight of agar -agar, 200 parts by weight of potato extract one, 5 parts by weight of malt, 15 parts by weight dextrose, 5 parts by weight of peptone, 2 parts Na2HP04 by weight, 0.3 parts by weight Ca (No3) 2 per 1000 cm3 of water.
Stosunek mieszaniny rozpuszczalników do po¬ zywki: 2 czesci wagowe mieszaniny ¦ rozpuszczalni- ków, 100 czesci wagowych pozywki agarowej.The ratio of the solvent mixture to the volume nutrients: 2 parts by weight of a mixture of 100 parts by weight of agar medium.
Sklad mieszaniny rozpuszczalników: 0,19 czesci wagowych dwumetyloformamidu lub acetonu, 0,01 czesci wagowych eteru alkiloarylopoliglikolowego jako emulgatora, 1,80 czesci wagowych wody — 40 razem 2 czesci wagowe mieszaniny rozpuszczalni¬ ków.Composition of the solvent mixture: 0.19 parts by weight of dimethylformamide or acetone, 0.01 parts by weight of alkylaryl polyglycol ether as an emulsifier, 1.80 parts by weight of water - 40 parts by weight of the solvent mixture in total cows.
Dawke substancji czynnej potrzebna do osiagnie¬ cia zadanego stezenia substancji czynnej w po¬ zywce miesza sie z podana iloscia rozpuszczalnika. 45 Koncentrat miesza sie dokladnie w'podanym sto¬ sunku wagowym z ochlodzona do temperatury 42°C ciekla pozywka i wylewa do naczynka Pe- triego o srednicy 9 cm. Ponadto przygotowuje sie naczynka kontrolne bez domieszki preparatu. Po ochlodzeniu i zestaleniu sie pozywki zakaza sie podanymi w tablicy rodzajami grzybów i inkubu¬ je w temperaturze okolo 21°C.The dose of active ingredient needed to be achieved desired concentration of active ingredient at the nutrient solution is mixed with the given amount of solvent. 45 The concentrate is thoroughly mixed in the given table weight ratio with cooled to temperature 42 ° C liquid culture medium and poured into the Pe- a tri with a diameter of 9 cm. Moreover, he is preparing himself control vessels without admixture of the preparation. After cooling and solidification of the medium is prohibited the types of mushrooms and incubus given in the table at a temperature of around 21 ° C.
Ocene prowadzi sie na podstawie szybkosci roz¬ woju grzybów po 4—10 dniach. Porównuje sie pro¬ mieniowy rozrost grzybni w traktowanych podlo¬ zach z rozrostem grzybni w pozywkach kontrol¬ nych.The evaluation is carried out on the basis of the speed of development mushroom farm after 4-10 days. Compares the prop mycelial growth in the treated media West with mycelium growth in control media all.
Bonitacje prowadzi sie za« pomoca liczb umow¬ nych o nastepujacym znaczeniu: 1 — brak rozro¬ stu grzyba, do 3 — silne hamowanie rozrostu, do — srednie hamowanie rozrostu, do 7 — slabe hamowanie rozrostu, 9 — rozrost taki sam, jak w próbie kontrolnej. \ W tablicy 6 podaje sie substancje czynne, ste¬ zenie substancji czynnych oraz uzyskane wyniki.ii moi Tablica 6 Testowanie rozwoju grzybni 14 Substancja czynna .2 •- ca s 41 61 Si Zwiazek o wzorze 6 Zwiazek o wzorze 8 Zwiazek o wzorze 13 Zwiazek o wzorze 10 Zwiazek o wzorze 11 Zwiazek q wzorze 1 Zwiazek o wzorze 12 .(znany) Zwiazek o wzorze 4 (znany) Przyklad VII. Badanie odpornosci krzyzo¬ wej w stosunku do BCM (beruzimidazolilokarba- minian metylu) na plytkach z Colletotrichum cof- feanum.Bonitations are carried out by means of contract numbers with the following meaning: 1 - no development one hundred mushrooms, up to 3 - strong growth inhibition, up to - moderate growth inhibition, up to 7 - weak growth inhibition, 9 - growth the same as in control sample. \ Table 6 lists the active ingredients, ste the active substances and the results obtained ii my Table 6 Testing the development of mycelium 14 Substance open .2 • - ca s 41 61 Si Compound of formula 6 Compound of formula 8 Compound of formula 13 Compound of formula 10 Compound of formula 11 Compound q in formula 1 Compound of formula 12 .(known) Compound of formula 4 (known) Example VII. Cross resistance test in relation to BCM (beruzimidazolylcarb- methyl minate) on plates with Colletotrichum cof- feanum.
Do próby stosuje sie szczepy Colletotrichtim cof- feanum wrazliwe lub odporne na dzialanie BCM lub preparaty wydzielajace BCM.For the test, strains of Colletotrichtim cof- feanum sensitive or resistant to BCM or BCM secreting preparations.
Opis metody. Jako pozywlke stosuje sie de^kstro- ze ziemniaczana — agar w skladzie: wyciag ziem¬ niaczany 4 g, D(+) jgjLikaza 20 g, pepton 10 g, slód g, agar — agar 20 g i woda do 1000 ml. Ciekla pozywke w ilosci 400 cm3 zawierajaca dekstroze ziemniaczana i agar, ochlodzona do temperatury 45°C, dokladnie miesza sie z 6 cm3 zawiesiny za¬ rodników Colletotrichum ooffeanum o stezeniu 1 000 000 zarodników/ml i w ilosci po 20 cm8 wy¬ lewa do plytek Petriego o srednicy 9 om. Z pre¬ paratów porównawczych oraz preparatów wedlug wynalazku otrzymuje sie koncentraty o stezeniu 000 ppm. Do rozpuszczenia preparatu stosuje sie mieszanine 4T°/o acetonu, 47% dwumetyloformami- du i 6°/o eteru alkiloarylopoligliikolowego jako e- mulgatora.Description of the method. As a medium, a special from potato - agar in the composition: extract of earth nate 4 g, D (+) jgjLikase 20 g, peptone 10 g, malt g, agar - 20 g agar and water to 1000 ml. Ciekla 400 cc of nutrient medium containing dextrose potato and agar, cooled to temperature 45 ° C, it is thoroughly mixed with 6 cm3 of the suspension Colletotrichum ooffeanum radicals at the concentration 1,000,000 spores / ml and 20 cm3 each left for Petri dishes with a diameter of 9 ohms. With pre¬ comparative samples and preparations according to of the invention, concentrates of a concentration are obtained 000 ppm. Use to dissolve the preparation a mixture of 4T% acetone, 47% dimethylform du and 6% alkylaryl polyglycol ether as e- emulsifier.
Koncentraty rozciencza sie woda do stezen 5000, 1000, 100, 50, 25 i 10 ppm. Do tak otrzymanych preparatów roboczych zanurza sie krazki bibuly filtracyjnej o srednicy 10 mm firmy Schleicher i Schiill i 4 krazki z 4 róznymi stezeniami wykla¬ da sie na plytce agarowej. Z tablicy wynika, ze na plytkach, na których wylozono krazki o steze¬ niach 10 000—100 ppm BCM lub cypendazolu nie stwierdzono rozwoju grzybni szczepów podatnych.Concentrates are diluted with water to concentrations of 5000, 1000, 100, 50, 25 and 10 ppm. To so received of working specimens, the blotting discs are immersed filter with a diameter of 10 mm from Schleicher and Schiill and 4 disks with 4 different concentrations of hatch can be done on an agar plate. The table shows that on plates, on which discs with a hole are placed 10,000-100 ppm of BCM or no cypendazole mycelium development of susceptible strains was found.
W próbie z tymi samymi preparatami i tym samym szczepem grzyba przy stezeniu 10 ppm stwierdzo¬ no dajace sie zmierzyc ogniska zahamowan. U szczepów odpornych BCM w stezeniach do 10 000 ppm nie dal zadnego dzialania, natomiast cypen- dazol w stezeniu od 5000 ppm dal male ognisko zahamowania wzrostu. W porównaniu z tym srod¬ ki wedlug wynalazku • w badanych stezeniach ha- mowaly prawie równie silnie rozwój szczepu za¬ równo podatnego, jak i odpornego. Otrzymany wynik potwierdza,, ze badane srodki wedlug .wy¬ nalazku nie wykazuja odpornosci krzyzowej w stosunku do BCM lub preparatów tworzacych 40 BCM.In an attempt with the same preparations and the same the fungus strain at a concentration of 10 ppm was found unmeasurable foci of inhibitions. AT BCM-resistant strains at concentrations up to 10,000 ppm did not have any effect, while cypen- dazol at a concentration of 5000 ppm for a small focus stunted growth. Compared to this Wednesday according to the invention • in the tested concentrations of ha- the development of the strain of za¬ equally compliant and resistant. Received the result confirms, that the tested means according to of the invention do not show any cross resistance in relation to BCM or forming preparations 40 BCM.
Nastepujace przyklady blizej wyjasniaja sposób wytwarzania, substancji czynnej srodka wedlug wynalazku. 45 Przyklad VIII. Wytwarzanie zwiazku o wzo¬ rze liO.The following examples explain the method manufacturing, the active ingredient of the agent according to invention. 45 Example VIII. Preparation of the compound of formula o. o.
Miesza sie w ciagu 22 godzin 60 g jedinowodziamu* soli sodowej 3-coK;yjanopentylo-2,4-«dwuketo-1^2,3,4- ^zterowodoro-(syim-triazyno-fl^-aI-Jbeiizimi 50 50(0 ml acetonitrylu i 65 g chlorku 'trójbutylocyny.Mixes in 22 hours 60 g of monkshood * 3-coK sodium salt; yano-pentyl-2,4- β-dio-1,2,3,4- ^ tetrahydro- (syim-triazine-fl ^ -aI-Jbeiizimi 50 50 (0 ml of acetonitrile and 65 g of tributyltin chloride.
, Osad odsacza sie, mieszanine reakcyjna rozpuszcza sie w 4 litrach chloroformu i saczy sie. Roztwór oczyszcza sie weglem kostnym, po czym odparowu¬ je i otrzymana pozostalosc rozciera sie z eterem 55 buitylowyim. Otrzymuje sie 74,3 g 1-lrójbuitylostan- nylo-3 -co^cyjanopentyio-2l,4-dwuketo-1,2,3,4-cztero - wodoro-sym-triazyno-[l^^a]-lbenzimidozolu o tem- y \ peraturze topnienia 110£°C., The precipitate is filtered off, the reaction mixture dissolves in 4 liters of chloroform and sift. Solution it is cleaned with bone carbon and then evaporated them and the resulting residue is rubbed with ether 55 buitylowyim. 74.3 g of 1-tritibitylostan are obtained nyl-3-co-cyanopentyio-2l, 4-dice-1,2,3,4-four- hydrogen-sym-triazino- [l ^^ a] -lbenzimidozole at the mp 110 ° C.
Obliczono 55^/o C, otrzymano: 50y3°/<»C. . 60 Wytwarzanie pólproduktu o wzorze 24. W 4 li¬ trach alkoholu ogrzewa sie do wrzenia w ciagu 4 godzin 286 g 3-w-cyjanopentylo-2,4-dwuketo-l,2,3, 4-czterowodoiro-sym-/triazyno-[ill2-a]-ibenzimidazolu i 39 g wodorotlenku sodu. Roztwór saczy sie na os goraco i zalteza do objejtosci 1 litra. Krystalizuje38703 is 16 Tablica 7 Badanie odpornosci krzyzowej w stosunku do BCM (benzimidazolilokarbaminian metylu) w próbie na plytce z Colletotrichum coffenaum Substancja czynna Zwiazek o wzorze 22 (BCM) Zwiazek o wzorze 23 [(cypendazol) Zwiazek o wzorze 7 Zwiazek o wzorze 6 BCM i cypendazol szczep odporny plytka 1 stezenie w ppm 000 0 X 5000 0 8 12 14 1000 0 0 11 100 0 0 4 7 plytka 2 stezenie w ppm 100 0 0 8 o m 0 0 3 6 CU 0 0 2 o 1—1 0 0 1 4 BCM i cypendazol szczep podatny plytka 1 000 X A 13 13 stezenie w ppm 5000 X X 1000 X X 9 9 o o X X 4 plytka 2 - stezenie w ppm 100 .X X o lO X 12 4 m c-. 11 9 2 4 o 1—1 7 0 3 Pomiar ogniska zahamowania rozwoju w mm.Calculated 55 ° C. Found: 50-3 ° C. . 60 Preparation of the intermediate of formula 24. In 4th November The drink of alcohol is heated to boiling within 4 hours 286 g 3-w-cyanopentyl-2,4-diceto-1,2,3, 4-tetrahydro-sym- / triazino- [ill2-a] -ibenzimidazole and 39 g of sodium hydroxide. The solution is sucked on the axis is hot and depends up to 1 liter. Crystallizes 38703 is 16 Table 7 Cross-resistance test against BCM (Benzimidazolylcarbamate methyl) in a test on a plate from Colletotrichum coffenaum Substance open Compound of formula 22 (BCM) Compound of formula 23 [(cypendazole) Compound of formula 7 Compound of formula 6 BCM and cypendazole strain resistant plate 1 concentration in ppm 000 0 X 5000 0 8 12 14 1000 0 0 11 100 0 0 4 7 plate 2 concentration in ppm 100 0 0 8 about m 0 0 3 6 CU 0 0 2 about 1–1 0 0 1 4 BCM and cypendazole strain susceptible plate 1 000 X AND 13 13 concentration in ppm 5000 X X 1000 X X 9 9 about about X X 4 plate 2 - concentration in ppm 100 .X X about 10 X 12 4 m c-. 11 9 2 4 about 1–1 7 0 3 Measurement of the growth inhibition focus in mm.
X = calkowite zahamowanie. jednowodzian soli sodowej 3- -dwuketo-l^^-c zterowodOTOnsym^triazymo- [ 1,2- -a]^beinzimidazolu, który oddziela sie. Przez zate- zenie lugu macierzystego otrzymuje sie druga frakcje krysztalów.X = complete inhibition. sodium salt monohydrate 3- -duketo-l ^^ - c z tetrahydrotone ^ triazymo- [1,2- -a] ^ beinzimidazole which separates. By zate- the second is obtained crystal fractions.
\ Wydajnosc: 288 g po wysuszeniu w temperatu¬ rze 1|00°C/0,1 tor. Widmo w podczerwieni w KBr: pasma przy 1560, Ii59i5, 1620, 1720 i 2240 cm-1.Yield: 288 g after temperature drying 1 | 00 ° C / 0.1 torr. Infrared spectrum in KBr: bands at 1560, Ii59i5, 1620, 1720 and 2240 cm-1.
S-toHCyjanopentylo^j^^dwuiketoHl^jS^-czterowo- doro-sym-triazyno-]'l,2-a[-(benzimidaizoil o tempera¬ turze topnienia 25B°C otrzymuje sie przez dziala¬ nie wejgianu dwufenylu na l-(benzimidazolilo-2)-3- (co-cyjanopentylo)Hmocznik o temperaturze topnie¬ nia >330°C Pochodna mocznika otrzymuje sie we¬ dlug opisu patentowego Sit. Zjedn. Am. nr 3 399 2,12 pnzez przegrupowanie Mco-cyjanopentylokarbamo- ilo)-2-aminobenzimida'zolu znanego z opisu paten¬ towego St. Zjedn. Am. nr 3 673 2/10.S-toHCyanopentyl ^ j ^^ diiketoHl ^ jS ^ -four- doro-sym-triazine-], 2-a [- (benzimidaisooyl, temp. The melting point of 25 ° C is obtained by treatment non-diphenyl at 1- (benzimidazolyl-2) -3- (co-cyanopentyl) H urea, m.p. > 330 ° C. The urea derivative is obtained as patent debt of Sit. US Am. No. 3 399 2.12 due to the rearrangement of Mco-cyanopentylcarbamo- yl) -2-aminobenzimidazole known from US Pat of St. US Am. no. 3 673 2/10.
• Przyklad IX. Wytwarzanie zwiazku o wzo¬ rze 1;5.• Example IX. Preparation of the compound of formula rze 1; 5.
Traktuje sie, jednoczesnie chlodzac, 28,2 g 3-co- -anetok!sy-karbotnylopentylo-2,4^dwuketo-!l,2,3,4- -czterowodOTO-sym-itriazyno-Iil^-a] -taizimidazolu w 400 g sulfotenu dwumetylowego 3,4 g wodoro¬ tlenku sodu rozpuszczonego w 20 ml wody. Pod cisnieniem 1/3 tor oddestylowuje sie okolo 126 g rozpuszczalnika. Do pozostalosci dodaje sie 27,7 g chlorku dwubutylocymy i mieszanine reakcyjna utrzymuje sie w ciagu 11 godzin w temperaturze 45°C. Traktuje sie 1 litrem chloroformu, mjieszanine reakcyjna przemywa sie kilkakrotnie woda i odsa¬ cza sie nieprzereagowany metoksykarbonylopen- / tyloHdwu-czterowodorotriazynobenizylobenzimilda- zol. Roztwór chloroformowy oddestylowuje sie pod zmniejszonym cisnieniem. Pozostalosc rozpuszcza sie w 5.00 ml toluenu, roztwór oczyszcza sie i od¬ parowuje. Pozostalosc rozciera sde z metylocyklo- heksanem i suszy. Otrzymuje sie 25 g 1-trójbutylo- 40 45 50 55 60 stanimnylo^3-a;-metokisykarbonylopentylo-2,4Kiwu- ketoily2y3,4-czterowodoro-Bym-triazyno-[l^-a]-ben- zimidazolu o temperaturze topnienia 1/06°C.Treat while cooling, 28.2 g 3-co- -anetok! sy-carbotnylpentyl-2,4- doublet-1,2,3,4- - tetrahydro-symtriazine-11 -a] -taizimidazole per 400 g of dimethyl sulfotene, 3.4 g of hydrogen sodium oxide dissolved in 20 ml of water. Under With a pressure of 1/3, about 126 g of the toroid are distilled solvent. 27.7 g are added to the residue dibutylcyl chloride and reaction mixture stays at the temperature for 11 hours 45 ° C. It is treated with 1 liter of chloroform, mixed with The reaction mixture is washed several times with water and filtered off there is unreacted methoxycarbonylene- / tyloHtwo-tetrahydrotriazinobenizylbenzimilda- sol. The chloroform solution is distilled off under reduced pressure. The residue dissolves in 5.00 ml of toluene, the solution is purified and dried evaporates. Triturate the residue with methylcyclo- hexane and dried. One obtains 25 g of 1-tributyl 40 45 50 55 60 stanimnyl ^ 3-a; -methoxycarbonylpentyl-2,4Kiwu ketoyl2y3,4-tetrahydro-Bym-triazino- [l ^ -a] -ben- Zimidazole with a melting point of 1/6 ° C.
Stosowany jako zwiazek wyjsciowy 3-cw-meto- ksykarbonylo-pentylo-2,,4niwuketo-ii,2,3,4-czterowo- doro-sym-triazyno-[il,,2-a]-benzimidazol o tempera¬ turze topnienia 221°C otrzymuje sie przez reakcje l-i(ibenzimidazolilo-2)^3-(w-metoksy1karbo(nylopen- ty11o)Hmocznika o temperaturze topnienia >330°C z weglanem dwufenylowym w temperaturze 160°C.Used as a 3-cw-method starting compound xycarbonyl-pentyl-2,4,4-nuketo-ii, 2,3,4-four- doro-sym-triazino- [il, 2-a] -benzimidazole, temperature mp 221 ° C is obtained by reactions 1- i (i-benzimidazolyl-2) ^ 3- (n-methoxy-carbo (nylopen- ty11o) H urea with a melting point> 330 ° C with diphenyl carbonate at 160 ° C.
Anologicznie wytwarza sie nizej podane zwiazki: ^ zwiazek o wzorze 11 o temperaturze topnienia 1)12°C, zwiazek o wzorze 8 o temperaturze topnie¬ nia 84°C, zwiazek o wzorze 25 o temperaturze top¬ nienia 148°C, zwiazek o wzorze 9 o temperaturze topnienia l|3i20C i zwiazek o wzorze 7, widmo w podczerwieni (KBr) 1560 cm-1.The following compounds are produced anologically: ^ the compound of formula 11 having a melting point 1) 12 ° C, the compound of formula VIII, mp 84 ° C, the compound of formula 25, mp at 148 ° C, the compound of formula 9 at temperature Melting point 13 ° C and the compound of formula 7, spectrum in infrared (KBr) 1560 cm-1.
Wytwarzanie 3^dwumetyloa/mino-^,4-dwuketo-l, 2y3,4Hczterowodoro-symMtriazyno-[ilir2-a]Hbeinzimida- zolu o wzorze 26 stosowanego jako pólprodukt.Preparation of 3-dimethylalmino-1, 4-dimethyl-1,4-dio-l, 2y3.4H-tetrahydro-symMtriazino- [ilir-2-a] Hbeinzimida- sol of formula 26 used as an intermediate.
Utrzymuje sie w temperaturze 16lO°C w ciagu 24 godzin 394 g l,l^dwumetylo^H(ibenzimidazoililo-)- -semikarbazydu, 428 g weglanu dwufenylowego, 650 g benzonitrylu i 2200 g fenolu. Wiekszosc mie¬ szaniny benzonitrylu i fenolu oddestylowuje sie pcd cisnieniem 13 tor. Do pozostalosci wprowadza sie 900 ml acetonitrylu. Krystalizat oddziela sie, przemywa acetronitrylem i woda i nastepnie su¬ szy w temperaturze 100°C/3 tor. Otrzymuje sie 360 g surowego 3-dwumetyloaminoH2,4-dwuketo-l, ^,3/,4Hczterowodoro^syim^triazyno^[l,2-a]4>enizimi- dazolu. W celu oczyszczenia zwiazek ten rozpuszcza sie we wrzacej mieszaninie skladajacej sie z 5 li¬ trów wody, 3 litrów alkoholu i 88 g wodorotlen¬ ku potasu. Roztwór saczy sie na zimno. Przesacz doprowadza sie do wartosci pH 4. Osad oddziela sie i wymywa z niego sole. Wydajnosc wynosi98703 1T 18 308 g oczyszczonego 'zwiazku. Temperatura top¬ nienia >3i30oC.Stays at 1610 ° C for 24 hours 394 g 1,14 dimethyl H (ibenzimidazoyl-) - -semicarbazide, 428 g of diphenyl carbonate, 650 g of benzonitrile and 2200 g of phenol. Most have the gas of benzonitrile and phenol is distilled off pcd with a pressure of 13 torr. He introduces the rest 900 ml of acetonitrile. The crystallization separates, washed with acetronitrile and water and then dried at 100 ° C / 3 torr. I get 360 g of crude 3-dimethylaminoH2,4-biceto-l, ^, 3 /, 4H, tetrahydro-triazine [1,2-a] 4> enizimi- dazol. It dissolves this compound to purify it in a boiling mixture consisting of 5 leaves liters of water, 3 liters of alcohol and 88 g of hydroxide towards potassium. The solution is sipped cold. Filtrate the pH is adjusted to 4. The precipitate is separated it is washed and the salts are washed out. The yield is 98703 1T 18 308 g of the purified compound. Mp temperature temperatures> 3 and 30oC.
Obliczono: 28,56% N, otrzymano: 28,5w/o N.Calculated: 28.56% N, found: 28.5 w / o N
Widmo w podczerwieni w KBr wykazuje silne pasma karbonylowe przy 1620—1640 cm-1, 1675 — 5 17i05 cm-1 i 1745 cm-1.The infrared spectrum of KBr shows strong carbonyl bands at 1620-1640 cm-1, 1675-5 17i05 cm-1 and 1745 cm-1.
Wytwarzanie l;l-dwumetylo-4-(benzimidazolilo- ^2)Hsemikarbazydu o wzorze 27 stosowanego jako pólprodukt.Preparation of l; l-dimethyl-4- (benzimidazolyl- ^ 2) Hsemicarbazide of Formula 27 used as intermediate.
Mieszanine 3 moli estru fenylowego kwasu ben- 10 zimidaizol(ilon2'-lkaribaminowego i 2100 g fenolu mie¬ sza sie z 24i0 g N1, N^wumetylohydrazyny w ciagu 7 godzin w temperaturze 70°C. Mieszanine reakcyjna^ saczy sie i zateza pod zmniejszonym ci- tonitrylu i chlodzi sie do temperatury 0°C. Kry- 15 sztaly oddziela sie, przemywa sie acetonitrylem i woda do której dodano mala ilosc srodka powierz¬ chniowo czynnego. Krysztaly suszy sie w tempera¬ turze liftO°C/3 tor. Otrzymuje sie 573 g 1,1-dwume- tylo-4d(benzimidazolilo-2)-sem!ikarbazydu o tempe- 20 raturze topnienia >3i3)0oiC.A mixture of 3 moles of ben-10 acid phenyl ester Zimidaisole (2'-carbamate ilon and 2100 g of copper phenol) it comes from 24.10 g of N1, N ^ vumethylhydrazine in 7 hours at 70 ° C. Mixture reaction is filtered and concentrated under reduced pressure tonitrile and cooled to 0 ° C. Kry- 15 The easels are separated, washed with acetonitrile and water to which a small amount of the agent has been added in operation. The crystals are dried at temperature liftO ° C / 3 track. Yield 573 g of 1,1-dimethyl tyl-4d (benzimidazolyl-2) -sem! icarbazide at a temperature of 20 with a melting point> 3i3) 0oC.
Widmo w podczerwieni produkitu sprasowanego z KBr wykazuje miedzy innymi silne pasma przy 151(2 i 1675 cm-1.The infrared spectrum of the product pressed from KBr shows, inter alia, strong bands at 151 (2 and 1,675 cm-1.
Wedlug przykladów VIII i IX otrzymuje sie tez 25 nastepujace zwiazki: zwiazek o wzorze 6 o tem¬ peraturze topnienia 182°C (rozklad)., widmo w pod¬ czerwieni (CHCI3): 1568, 1585, 1605, 1622, 1660, 1730 cm-1, zwiazek o wzorze 28 po jednorazowym przekrystalizowaniu z toluenu i jednokrotnym z 30 acetonu temperatura topnienia wynosi 100°C (roz¬ klad), widmo w podczerwieni (CHCI3): 1562, 1580, 1602, 16)18, 1665, 11(7.25 cm"1, zwiazek o wzorze 16 o temperaturze topnienia 164°C po przekrystalizo¬ waniu z acetonitrylu, (stosowany jako zwiazek wyjsciowy 3-metylo-294-dwuketo-l,2,3,4-czterowo- doiro^sym^triazyno-[lv2-a]-benzimidazol jest znany z opisu RFN DOS nr 2, l)44i 505), zwiazek o wzorze 17 o temperaturze topnienia 136°C z acetonitrylu (stosowany jako zwiazek wyjsciowy 3-fenylo-2,4- -dwuketoHl^^-czterowodoro-sym-triazyno-fl^-a] ^benzimidazoi jest znany z opisu RFN DOS' nr 2 144 5(05 zwiazek o wzorze 17 o temperaturze top¬ nienia167°C po przekryistalizowaniu z acetonitrylu) stasowany jako zwiazek wyjsciowy 3--tetradecylo- - 45 ^^-dwuketo-il^^^-czterowodoroHsym-triazyno- -[ily2-a]-benzimidazol o temperaturze topnienia 19i3°C otrzymuje sie przez reakcje l-(benzi.midazo- lilo-2)^Metradecylomocznika z weglanem dwufe- nylowym; Mbenzi!midazolilo-2,)-3-tetradecylomo- 50 cznik, otrzymuje sie przez reakcje 2-aminobenzi- midazolu z izocyjanianem tetradecylu w ksylenie w temperaturze okolo lft0°C), zwiazek o wzorze 19 o temperaturze topnienia 14/1°C (rozklad), (stoso¬ wany jako zwiazek wyjsciowy 3-cykloheksylo-2,4- 55 ^dwulketo-il^ySi^^czterowodoro-symHtriazyno-Cl^- -a]-benzimidazol o temperaturze topnienia 335°C otrzymuje sie z lH(ibenzimodazolilo-2-(3^cykohekisy- lomocznJka i weglanu dwufenylowego; l-(benzimi- dazolilOn2)-3^cyklohe(ksylomocznik otrzymuje sie z 80 2-aminobenzi)midozolu i izocyjanianu cykloheksy- u w ksylenie w temperaturze okolo 12i0°C), zwia¬ zek o wzorze 20 o temperaturze tolpnienia 124°C, po przekrystalizowainiu z acetonitrylu, (stosowany 40 jako zwiazek wyjsciowy 3^(2-fenyloetylo)-2„4-d(WU- keito-,li^v3,4^czterowodoro-symHtriazyno [ly2^a]-ben- zimidazol (temperatura topnienia 298°C z dioksa¬ nu) wytwarza sie z weglami dwufenylowego i 1- -i(benzimidazolilo-2)-3-i(2-!fenyloetylo)^m«ocznijkab który z kolei wytwarza sie z v estru fenylowego kwaisu N4>enzimiidazolilo-(2)-karba!minowego i 2- -fenyloetyloaminy) oraz zwiazek o wzorze 21 o temperaturze topnienia okolo 1&3°C po przekrysta¬ lizowaniu z 2^metoksyetanolu, wiiimo w podczer¬ wieni (KBr): 1555, 1575, 1(6,12, 162$, (H7&2, 3200 cm"1, (stosowany jako zwiazek wyjsciowy 3-(w-metylo- aminokairboinylopenityilo)-i2i,4-dwu^keto-rl,2,3,4Hczte- rowodoro-sym-triazyno- [1,2-a]nbenzimidazol (tem¬ peratura topnienia 268°C z rozkladem z butanolu), otrzymuje sie przez ogrzewanie 3^(wHmetoksykar- bonylopentylo)-2,4-dwuketoJl^,3|,4-czterowodoro- -sym-triazyno^Ol ,2^a]nbenzimidazolu (temperatura topnienia 221°C) z metyloamina w mieszaninach butanol-woda).According to examples VIII and IX, you also get 25 the following compounds: a compound of formula 6 with a temperature of mp 182 ° C (decomposition), spectrum as shown below Red (CHCI3): 1568, 1585, 1605, 1622, 1660, 1730 cm-1, the compound of formula 28 after a single use recrystallization from toluene and once from 30 acetone, the melting point is 100 ° C. (dil clade), infrared spectrum (CHCl3): 1562, 1580, 1602, 16) 18, 1665, 11 (7.25 cm -1, the compound of formula 16 o 164 ° C. after recrystallization with acetonitrile (used as a compound output 3-methyl-294-biceto-1,2,3,4-four- doiro-sym- triazino- [lv2-a] -benzimidazole is known from German DOS description No. 2, l) 44 and 505), a compound of formula 17, m.p. 136 ° C from acetonitrile (used as starting compound 3-phenyl-2,4- -duketoHl ^^ - tetrahydro-sym-triazine-fl ^ -a] ^ benzimidazoi is known from the German description DOS 'no 2 144 5 (05 compound of formula 17, m.p. temperature 167 ° C after recrystallization from acetonitrile) Tied as starting compound 3 - tetradecyl- - 45 ^^ - two-e-il ^^^ - tetrahydroHsym-triazine- - [ily2-a] benzimidazole, m.p. 19 and 3 ° C is obtained by the reactions 1- (benzimidazo- lyl-2) ^ Metradecylurea with bicarbonate nylon; Mbenzi! Midazolyl-2,) - 3-tetradecylomo- 50 chemical, obtained by reactions 2-aminobenzi midazole with tetradecyl isocyanate in xylene at about 1ft0 ° C), the compound of formula 19 with a melting point of 14/1 ° C (decomposition), (comp Important as a starting material 3-cyclohexyl-2,4- 55 ^ dulketo-yl ^ ySi ^^ tetrahydro-symHtriazine-Cl ^ - - a] -benzimidazole, m.p. 335 ° C is obtained from lH (ibenzimodazolyl-2- (3 ^ cyclohekisy- lurea and diphenyl carbonate; l- (benzimi- dazolylOn2) -3-4 cyclohe (xylurea is obtained from 80 2-aminobenzi) midozol and cyclohexyl isocyanate in xylene at a temperature of about 12-10 ° C), comp formula 20 with a melting point of 124 ° C, after recrystallization from acetonitrile, (used 40 as starting compound 3 ^ (2-phenylethyl) -2'4-d (WU- keito-, li ^ v3,4 ^ tetrahydro-symHtriazino [ly2 ^ a] -ben- Zimidazole (m.p. 298 ° C. from dioxa nu) is prepared with diphenyl and 1- -i (benzimidazolyl-2) -3-i (2-! phenylethyl) ^ m which in turn is prepared from the phenyl ester v N4 acid> enzimiidazolyl- (2) -carbine and 2- -phenylethylamine) and the compound of formula 21 o melting point about 1-3 ° C after crystallization lysis with 2-methoxyethanol, also in the infrared zircon (KBr): 1555, 1575, 1 (6.12, 162 $, (H7 & 2, 3200 cm "1, (used as starting compound 3- (n-methyl- aminocairboinylpenityl) -i2i, 4-di-keto-R1, 2,3,4H hydrogen-sym-triazino [1,2-a] n-benzimidazole (temp melting point 268 ° C with decomposition from butanol), obtained by heating 3 ° C (in H-methoxycar- bonylopentyl) -2,4-di-eoI ^, 3 |, 4-tetrahydro -sym-triazino, O1, 2 [alpha]] n-benzimidazole (temp mp 221 ° C) with methylamine in the mixtures butanol-water).
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752528623 DE2528623A1 (en) | 1975-06-26 | 1975-06-26 | TIN-CONTAINING TRIAZINO-BENZIMIDAZOLES, PROCESS FOR THEIR MANUFACTURING AND USES AS INSECTICIDES, ACARICIDES AND FUNGICIDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| PL98703B1 true PL98703B1 (en) | 1978-05-31 |
Family
ID=5950048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL1976190711A PL98703B1 (en) | 1975-06-26 | 1976-06-25 | INSECTICIDAL, MUSHROOM AND MUSHROOM AGENT |
Country Status (20)
| Country | Link |
|---|---|
| US (1) | US4026934A (en) |
| JP (1) | JPS523098A (en) |
| AT (1) | AT341541B (en) |
| AU (1) | AU1511976A (en) |
| BE (1) | BE843340A (en) |
| BR (1) | BR7604158A (en) |
| DD (1) | DD127067A5 (en) |
| DE (1) | DE2528623A1 (en) |
| DK (1) | DK286776A (en) |
| EG (1) | EG12059A (en) |
| ES (1) | ES449234A1 (en) |
| FR (1) | FR2317305A1 (en) |
| GB (1) | GB1519687A (en) |
| IL (1) | IL49887A0 (en) |
| LU (1) | LU75236A1 (en) |
| NL (1) | NL7606854A (en) |
| PL (1) | PL98703B1 (en) |
| PT (1) | PT65266B (en) |
| SE (1) | SE7607220L (en) |
| TR (1) | TR18827A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4178382A (en) * | 1978-06-19 | 1979-12-11 | Uniroyal, Inc. | N-substituted triorganostannylhydro-carbylcarboxylic acid hydrazides |
| DE3324903A1 (en) * | 1983-07-09 | 1985-01-17 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF SUBSTITUTED ETHYLENE UREAS AND NEW N-VINYLETHYLENE UREAS |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3764678A (en) * | 1970-04-21 | 1973-10-09 | Ciba Geigy Corp | Organotin-substituted s-triazines for controlling insects, acarinal, fungi, bacteria, and mollusks |
| BE788015A (en) * | 1971-08-28 | 1973-02-26 | Bayer Ag | NEW INSECTICIDE AND ACARICIDE COMPOSITION |
| US3725406A (en) * | 1971-10-12 | 1973-04-03 | Univ California | Benzimidazole derivatives as fungicidal active compounds |
-
1975
- 1975-06-26 DE DE19752528623 patent/DE2528623A1/en active Pending
-
1976
- 1976-06-04 US US05/693,037 patent/US4026934A/en not_active Expired - Lifetime
- 1976-06-21 EG EG368/76A patent/EG12059A/en active
- 1976-06-22 AU AU15119/76A patent/AU1511976A/en not_active Expired
- 1976-06-23 IL IL49887A patent/IL49887A0/en unknown
- 1976-06-23 SE SE7607220A patent/SE7607220L/en unknown
- 1976-06-23 PT PT65266A patent/PT65266B/en unknown
- 1976-06-23 NL NL7606854A patent/NL7606854A/en not_active Application Discontinuation
- 1976-06-24 GB GB26285/76A patent/GB1519687A/en not_active Expired
- 1976-06-24 BE BE168251A patent/BE843340A/en unknown
- 1976-06-24 LU LU75236A patent/LU75236A1/xx unknown
- 1976-06-24 DD DD193549A patent/DD127067A5/xx unknown
- 1976-06-25 JP JP51074591A patent/JPS523098A/en active Pending
- 1976-06-25 AT AT465376A patent/AT341541B/en not_active IP Right Cessation
- 1976-06-25 FR FR7619319A patent/FR2317305A1/en not_active Withdrawn
- 1976-06-25 BR BR7604158A patent/BR7604158A/en unknown
- 1976-06-25 DK DK286776A patent/DK286776A/en unknown
- 1976-06-25 ES ES449234A patent/ES449234A1/en not_active Expired
- 1976-06-25 PL PL1976190711A patent/PL98703B1/en unknown
-
1977
- 1977-07-24 TR TR18827A patent/TR18827A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IL49887A0 (en) | 1976-08-31 |
| JPS523098A (en) | 1977-01-11 |
| AT341541B (en) | 1978-02-10 |
| TR18827A (en) | 1977-11-01 |
| FR2317305A1 (en) | 1977-02-04 |
| US4026934A (en) | 1977-05-31 |
| NL7606854A (en) | 1976-12-28 |
| ES449234A1 (en) | 1977-08-01 |
| BR7604158A (en) | 1977-07-26 |
| ATA465376A (en) | 1977-06-15 |
| GB1519687A (en) | 1978-08-02 |
| SE7607220L (en) | 1976-12-27 |
| DK286776A (en) | 1976-12-27 |
| DD127067A5 (en) | 1977-09-07 |
| AU1511976A (en) | 1978-01-05 |
| EG12059A (en) | 1979-03-31 |
| PT65266A (en) | 1976-07-01 |
| PT65266B (en) | 1977-12-07 |
| LU75236A1 (en) | 1977-03-16 |
| BE843340A (en) | 1976-12-24 |
| DE2528623A1 (en) | 1977-01-13 |
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